Substituted amidophenylthioureas

ABSTRACT

Amidophenylthioureas of the formula: IN WHICH EACH X independently stands for a halogen atom, alkyl with one to four carbon atoms or alkoxy with one to four carbon atoms, N STANDS FOR 0, 1 OR 2, R stands for alkyl with one to 12 carbon atoms, R&#39;&#39; stands for a hydrogen atom or alkyl with one to four carbon atoms, and R&#39;&#39;&#39;&#39; stands for a five- or six-membered heterocyclic radical which may contain one or more hetero-atoms selected from oxygen, sulfur and nitrogen atoms, which possess fungicidal properties and which may be produced by conventional methods.

ie Sites tet n 1 Widdig et ai.

I SUBSTHTUTED AMIDOPHENYLTHKOUREAS [75] Inventors: Arno Widdig;Engelbert Kuhle;

Klaus Sasse; Hans Scheinpflug; Ferdinand I Grewe; Hclmut Kaspers;Paul-Ernst Frohberger, all of Leverkusen, Germany [51] Int. Cl. ..C07d31/50 [58] Field of Search ..260/294.8 H, 347.2

[56] References Cited UNITED STATES PATENTS 3,642,891 2/1972 Teach..260/553 A 1M8ll'cll 13, 1973 [57] ABSTRACT Amidophenylthioureas of theformula:

in which each X independently stands for a halogen atom, alkyl with oneto four carbon atoms or alkoxy with one to four carbon atoms,

n stands for 0, l or 2, v r

R stands for alkyl with one to 12 carbon atoms,

R' stands for a hydrogen atom or alkyl with one to four carbon atoms,and

R" stands for a fiveor six-membered heterocyclic radical which maycontain one or more heteroatoms selected from oxygen, sulfur andnitrogen atoms, which possess fungicidal properties and which may beproduced by conventional methods.

5 Claims, N0 Drawings SUBSTITUTED AMIDOPHENYLTHIOUREAS The presentinvention relates to and has for its objects the provision of particularnew amidophenylthioureas which possess fungicidal properties, activecompositions in the form of mixtures of such compounds with solid andliquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating fungi, withother and further objects becoming apparent from astudy of the within specification and accompanying examples.

It is known that certain dithiocarbamates can be used as fungicides, forexample zinc ethylene-1,2bisdithiocarbamate (A) (see US. Pat. No.2,457,674). However, at low application concentrations the effectivenessof this compound is not always satisfactory.

The present invention provides amidophenylthioureas of the generalformula:

in which each X independently stands for a halogen atom, alkyl with oneto four carbon atoms or alkoxy with one to four carbon atoms,

n stands for 0,1 or 2,

R stands for alkyl with one to 12 carbon atoms,

R' stands for a hydrogen atom or alkyl with one to four carbon atoms,and

R" stands for a fiveor six-membered heterocyclic radical which maycontain one or more heteroatoms selected from oxygen, sulfur andnitrogen atoms.

The compounds of the formula (l) have been found to exhibit strongfungicidal properties.

The present invention also provides a process for the production of theamidophenylthioureas of the formula (I) in which a 2-aminoanilinederivative of the formula I'll in which X, n, R and R are the same asdefined above, is

reacted with an isothiocyanate of the formula ROOC-N=C=S (lll) in whichR is the same as defined above, in the presence of a diluent (which termincludes a solvent).

It is decidedly surprising that the thioureas according to the inventionexhibit a higher fungicidal activity than the above-mentioned zincethylene-l,Z-bis-dithiocarbamate. The compounds according to theinvention therefore represent a substantial enrichment of the art.

When 2-furoylaminoaniline and ethoxycarbonylisothiocyanate are used asstarting materials, the reaction course can be represented by thefollowing equation:

(Ila) The Z-aminoaniline derivatives are defined by the formula (II). Inthis formula, as in formula (I), X stands preferably for chlorine,bromine, fluorine, methyl, ethyl, isopropyl, n-butyl, methoxy, ethoxy orisopropoxy; n stands preferably for 0 or I; R stands preferably forhydrogen, methyl or ethyl; and R" stands preferably for 2-furyl,2-thienyl, 2-pyridyl, 3- pyridyl, 4-pyridyl or 4-thiazolyl.

The 2-aminoaniline derivatives used as starting materials are partiallyknown (see J. org. Chem. Vol 27 II, 2,163 (1962)). They can be obtainedby reduction or catalytic hydrogenation of the appropriate 2-nitroanilides.

As examples of the 2-aminoaniline derivatives, there may be mentioned:

Z-furancarboxylic acid thiophenecarboxylic picolinecarboxylic acid(2'-amino)-anilide, nicotinecarboxylic acid (2-amino)-anilideisonicotinecarboxylic acid (2-amino)-anilide and 4-thiazolecarboxylicacid (2'-amino)-anilide.

The isothiocyanates used as starting materials are defined by theformula (III). In this formula, as in formula (I), R stands preferablyfor methyl, ethyl or propyl. Some of the isothiocyanates are known [seeJ. Chem. Soc. 93, 696 (1908)]. They can also be obtained from thereaction between alkali methal isothiocyanates and haloformic acidesters.

As examples of the isothiocyanates which may be used in the process ofthe invention, there may be mentioned: methoxycarbonylisothiocyanate,ethoxycarbonylisothiocyanate, propoxycarbonylisothiocyanate andisopropoxycarbonylisothiocyanate.

When carrying out the process according to the invention, any inertorganic solvent is suitable as the diluent. These include for example:hydrocarbons, such as benzine, ligroin, hexane, benzene and toluene;chlorinated hydrocarbons, such as methylene chloride, chloroform, carbontetrachloride and chlorobenzene; ethers, such as diethyl ether, dibutylether, tetrahydrofuran and dioxane; ketones, such as acetone,methylisopropyl ketone and acetophenone, cyclohexanone; and any desiredmixtures of the said solvents.

The reaction temperature can be varied within a fairly wide range. Ingeneral, this work is carried out between about -l0 to C, preferablybetween about 0 to 40 C.

When carrying out the process according to the invention, l mole ofisothiocyanate is preferably used per 2- (2 '-amino)-anilide,

(2 '-amino)-anilide, acid mole of 2-aminoaniline derivative. Amountsgreater or lesser by up to percent are possible without substantialdiminution of the yield. When the reaction mixture is cooled, the endproducts are obtained in crystalline form and can be separated bysuction filtration and, optionally, purified by redissolving orrecrystallization.

A preferred embodiment of the process comprises preparing the requiredisothiocyanate from a haloformic acid ester and an alkali metalisothiocyanate in an inert solvent and, without isolating it, reactingit directly with the 2-aminoaniline derivative.

The active compounds according to the invention exhibit a strongfungitoxic activity. In the concentrations necessary for the control offungi, they do not damage cultivated plants, and have a low toxicity towarmblooded animals. For these reasons, they are suitable as cropprotection agents for the control of fungi. Fungitoxic agents in cropprotection are used for the control of Archimycetes, Phycomycetes,Ascomycetes, Basidiomycetes and Fungi Imperfecti.

The active compounds according to the invention have a very broadactivity spectrum and can be applied against parasitic fungi whichinfect above-the-soil parts of plants or attack the plants from thesoil, as well as against seed-borne pathogenic agents.

They are particularly effective against fungi which cause powdery mildewdiseases. To this group of fungi there belong predominantlyrepresentatives from the Erysiphaceae family with the most importantgenera being Erysiphe, Uncinula (Oidium), Sphaerotheca and Podosphaera.Important fungi include Erysiphe cichoracearum, Podosphaera leucotrichaand Uncinula necator.

The active compounds according to the invention also give good resultsin the control of rice diseases. Thus, they show an excellent activityagainst the fungi Piricularia oryzae and Pellicularia sasakii, by reasonof which they can be used for the joint control of these two diseases.This means a substantial advance, since, up to now, agents of differentchemical constitution were required against these two fungi.Surprisingly, the active compounds show not only a protective activitybut also a curative and systemic effect.

The active compounds according to the invention, however, also actagainst other fungi which infect rice or other cultivated plants, suchas, for example, Cochliobolus myiabeanus, Mycosphaerella musicola,Cercospora personata, Botrytis cinerea, Alternaria species, Verticilliumalboatrum, Phialophora cinerescens and Fusarium species as well asagainst the bacterium Xanthomonas oryzae.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e., plant compatible or herbicidally inert)pesticide diluents or extenders, i.e., diluents or extender of the typeusable in conventional pesticide formulations or compositions, e.g.,conventional pesticide dispersible carrier vehicles, such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders, oils,pastes, soluble powders, dusting agents, granules, tablets, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g., conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: inert dispersible liquid diluent carriers including inertorganic solvents and non-solvents such as aromatic hydrocarbons (e.g.,benzene, toluene, xylene, dimethyl napththalene, aromatic naphthas,etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g.,chlorobenzenes, etc.), paraffins (e.g., petroleum fractions),chlorinated aliphatic hydrocarbons (e.g., methylene chloride, etc.),alcohols (e.g., methanol, ethanol, propanol, butanol, etc.), amines(e.g., ethanolamine, etc.), ethers, etheralcohols (e.g., glycolmonomethyl ether, etc.), amides (e.g., dimethyl formamide, etc.),sulfoxides (e.g., dimethyl sulfoxide, etc.), ketones (e.g., acetone,etc.), and/or water; as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g., kaolins, alumina,silica, chalk, (i.e., calcium carbonate, talc, keselguhr, diatomaceousearth, clay, montmorillonite, etc.), and ground synthetic minerals(e.g., highly dispersed silicic acid, silicates, e.g., alkali silicates,etc.), whereas the following may be chiefly considered for use asconventional carrier vehicle assistants, e.g., surface-active agents,for this purpose: emulsifying or wetting agents, such as non-ionicand/or anionic emul sifying or wetting agents (e.g., polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfonates, aryl sulfonates, etc., and especially alkylaryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other fungicides, orherbicides, insecticides, acaricides, nematocides, bactericides, etc.,including, especially fungicidal, organophosphorus compounds, carbamatecompounds, dithiocarbamate compounds, chlorine compounds, dinitrocompounds, organic sulfur or copper compounds, substituted phenoxycompounds, chlorophenols, substituted diphenyl ethers, anilidecompounds, ureas, triazines, antibiotics, and other known agriculturalchemicals and/or fertilizers, if desired, or in the form of particulardosage preparations for specific application made therefrom, such assolutions, emulsions, suspensions, powders, pastes, and granules whichare thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.1-95 percent, andpreferably 2.0 percent, by weight of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.001-10 percent,preferably 0.01-5 percent, by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as (l) a dispersibleinert finely divided carrier solid, and/or (2) a dispersible liquid suchas an inert organic solvent and/or water preferably including asurface-active effective amount of a carrier vehicle assistant, e.g., asurface-active agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally about 0.0001- percent, andpreferably 0.0l1.0 percent, by weight of the mixture.

In the case of use as seed dressings, applied amounts of0.l to 10 g,preferably 0.2 to 2 g, of active compound per kg of seed are usuallysuitable.

In the case of use as soil treatment agents, applied amounts of 1 to 500g, preferably 10 to 200 g, per cubic meter of soil are necessary.

The active compounds according to the invention show also aninsecticidal and acaricidal activity as well as activity against somemold fungi and yeasts. in concentrations higher than those necessary forfungicidal use, the substances inhibit plant growth.

The active compounds can also be used in accordance with the well-knownultra'low-volume process with good success, i.e., by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, e.g., average particle diameter of from 50-100 microns; oreven less, i.e., mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about to about 95 percent by weight of theactive compound, or even the 100 percent active substance alone, e'.g.,about 20-100 percent by weight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling fungi, which comprise applying to atleast one of (a) such fungi and (b) their habitat, i.e., the locus to beprotected, a fungicidally effective or toxic amount of the particularactive compound of the the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by squirting, spraying,atomizing, vaporizing, scattering, dusting, watering, sprinkling,pouring, dressing, via incrustation; and the like.

Significantly, the fungicidal compositions of the present invention canbe applied for example by spraying a dust formulation directly ontostems and leaves of plants; or by using the formulation as aseed-dressing; by spraying an emulsifiable concentrate, diluted withwater, etc. to a desirable concentration, onto stems and leaves ofplants; by suspending a wettable powder in water at a desirableconcentration and spraying the formulation onto stems and leaves ofplants; by applying granule formulations to the soil; and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application, the purpose for which the activecompound is used, and the like. Therefore, in special cases, it ispossible to go above or below the aforementioned concentration rangesand dosage amounts per unit area.

The fungicidal effectiveness of the particular new compounds of thepresent invention is illustrated, without limitation, by the followingExamples:

EXAMPLE 1 Fusicladium test (systemic) Solvent: 4.7 parts by weightacetone Emulsifier: 0.3 parts by weight alkylaryl polyglycol etherWater: parts by weight The amount of active compound required for thedesired concentration of the active compound in the liquid to be usedfor watering is mixed with the stated amount of solvent, and theconcentrate is diluted with the stated amount of water which containsthe stated additions.

Apple seedlings grown in standard soil are, in the 3 4 leaf stage,watered once in one week with 20 cc of the liquid to be used forwatering, in the stated concentration of active compound, with referenceto cc of soil. The plants so treated are, after the treatment,inoculated with an aqueous conidium suspension of Fusicladiumdendriticum el and incubated for 18 hours in a humidity chamber at 18 20C and at a relative atmospheric humidity of 100 percent. The plants aresubsequently placed in a greenhouse for 14 days.

15 days after inoculation, the infection of the seedlings is determinedas a percentage of the untreated but also inoculated control plants. 0percent means no infection; 100 percent means that the infection isexactly as great as in the case of the control plants. a

The active compounds, the concentrations of the active compounds and theresults obtained can be seen from the following Table I:

TABLE 1 FUSICLADIUM TEST (SYSTEMIC) Infection as u pvruvntugu of EXAMPLE2 Erysiphe test Solvent: 4.7 parts by weight acetone Emulsifier: 0.3parts by weight alkylaryl polyglycol ether Water: 95.0 parts by weightThe amount of the active compound required for the desired concentrationof active compound in the spray liquid is mixed with the stated amountof the solvent, and the concentrate is diluted with the stated amount ofwater containing the stated additions.

Young cucumber plants with about three foliage leaves are sprayed withthe spray liquid until dripping wet. The cucumber plants remain in agreenhouse for 24 hours to dry. They are then, for the purpose ofinoculation, dusted with conidia of the fungus Erysiphe cichoracearum.The plants are subsequently placed in a greenhouse at 23 24 C and at arelative atmospheric humidity of about 75 percent.

After 12 days, the infection of the cucumber plants is determined as apercentage of the untreated but also inoculated control plants. percentmeans no infection; 100 percent that the infection is exactly as greatas in the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults obtained can be seen from the following Table 2:

TABLE 2 Erysiphe Test Infection as a percentage of the infection of theuntreated control with a concentration of active EXAMPLE 3 Erysiphetest/systemic Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 partsby weight alkylaryl polyglycol ether Water: 95 parts by weight Theamount of the active compound required for the desired concentration inthe liquid to be used for watering is mixed with the stated amount ofthe solvent, and the concentrate is diluted with the stated amount ofwater containing the stated additions.

Cucumber plants grown in standard soil are, in the oneto two-leaf stage,watered three times in one week with cc of the liquid to be used forwatering, in the stated concentration of active compound with referenceto 100 cc of soil.

The plants so treated are, after the treatment, inoculated with conidiaof the fungus Erysiphe cichoracearum. The plants are subsequently placedin a greenhouse at 2324 C and at a relative atmospheric humidity ofpercent.

After 12 days, the infection of the cucumber plants is determined as apercentage of the untreated but also inoculated control plants. 0percent means no infection; percent means that the infection is exactlyas great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults obtained can be seen from the following Table 3:

TABLE 3 l'lryslplm Test (systemic) Infection as a percentage of theinfection of the untreated control with a concentration of activeEXAMPLE 4 Agar plate test Test for fungitoxic effectiveness and breadthof the activity spectrum.

Solvent: acetone Parts by weight: a. 1000 To produce a suitablepreparation of the active compound 1 part by weight of the activecompound is taken up in the stated amount of solvent.

The preparation of the active compound is added to potato dextrose agar(which has been liquefied by heating) in such an amount that the desiredconcentration of active compound is set up therein. After thoroughshaking to achieve a uniform dispersion of the active compound, the agaris poured into Petri dishes under sterile conditions. When the mixtureof substrate and active compound has solidified, test fungi from purecultures are inoculated on to it in small discs of 5 mm diameter. ThePetri dishes remain at 20 C for 3 days for incubation.

After this time, the inhibiting action of the active compound on themycelium growth is determined in categories, taking into account theuntreated control. Zero means no mycelium growth, either on the treatedsubstrate or on the inoculum, the symbol means mycelium growth on theinoculum only no spread to the treated substrate; and the symbol meansmycelium growth from the inoculum on to the treated substrate, similarto the spread to the untreated substrate of the control.

The active compounds, the concentration of the active compounds, thetest fungi and the inhibition effects achieved can be seen from thefollowing Table 4:

TABLE 4 Agar Plate Test Concentration of active compound in the EXAMPLE6 Piricularia and Pellicularia Test substrate in SclcrotiniaThielaviopsis Fusarium Fusarium Active compound mg./liter sclerotiontmbasicola culmorum oxysporum Untreated (A) CHgNHCS-S 10 100 /Zn CHz-NH CS S (known) EXAMPLE 5 Seed dressing test/bunt of wheat (seed-bornmycosis) To produce a suitable dry dressing, the active compound isextended with a mixture of equal parts by weight of talc and kieselguhrto give a finely powdered mixture with the desired concentration of theactive compound.

Wheat seed is contaminated with 5 g of the chlamydospores of Tilletiacaries pe kg of seed. To apply the dressing, the seed is shaken with thedressing in a closed glass flask. The seed, on moist loam under a coverofa layer of muslin and 2 cm of moderately moist compost soil, isexposed to optimum germination conditions for the spores for days at 10C in a refrigerator.

The germination of the spores on the wheat grains, each of which iscontaminated with about 100,000 spores, is subsequently determinedmicroscopically. The smaller the number of spores which have germinated,the more effective is the active compound.

The active compounds, the concentrations of the active compounds in thedressing, the amounts of dressing used and the percentage sporegerminationcan be seen from the following Table 5:

TABLE 5 Seed dressing test/bunt of wheat 5 4 weeks old are sprayed withthe spray liquor until dripping wet. The plants remain in a greenhouseat temperatures of 22 to 24 C and a relative atmospheric humidity ofabout percent until they are dry. One batch of the plants is theninoculated with an aqueous suspension of 100,000 to 200,000 spores/ml ofPiricularia oryzae and placed in a chamber at 24 26 C and percentrelative atmospheric humidity. The other batch of the plants is infectedwith a culture of Pellicularia sasakii grown on malt agar and placed at28 30 C and 100 percent relative atmospheric humidity.

5 to 8 days after inoculation, the infection of all the leaves presentat the time of inoculation with Piricularia oryzae is determined as apercentage of the untreated but also inoculated control plants. In thecase of Concentration of the plants infected with Pellicularia sasakii,the infection on the leaf sheaths after the same time is also determinedin proportion to the untreated but infected control. percent means noinfection; 100 percent means that the infection is exactly as great inthe case of the control plants.

The active compounds, the concentrations of the active compounds and theresults obtained can 'be seen from the following Table 6:

TABLE 6 Piricularia (a) and Pellicularia (b) Test Infection as apercentage of the infection of the untreated control with aconcentratlon of nctlvc compound (in percent) of Active compound 0.050.025 0. 0. 025

(A) CII -NIlC S-S 26 75 25 100 100 /Zn CH1 NHC S-S (known) S O U l 0 l 0l 0 ll ll 1 0 1 75 NHC-NHCO Cells (1) Nll j l ll'otvclivv. I (umtivinEXAMPLE 7 Podosphaera test (powdery mildew of apples) [Protective]Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weightalkylaryl polyglycol ether Water: 95 parts by weight The amount ofactive compound required for the desired concentration of the activecompound in the spray liquid is mixed with the stated amount of solvent,and the concentrate is diluted with the stated amount of water whichcontains the stated additions.

Young apple seedlings in the 4 6 leaf stage are sprayed with the sprayliquid until dripping wet. The plants remain in a greenhouse for 24hours at C and at a relative atmospheric humidity of 70 percent. Theyare then inoculated by dusting with conidia of the apple powdery mildewcausative organism (Podosphaera leucotricha Salm.) and placed in agreenhouse at a temperature of 21 23 C and at a relative atmospherichumidity of about 70 percent.

10 days after the inoculation, the infestation of the seedlings isdetermined as a percentage of the untreated but also inoculated controlplants.

0 percent means no infestation; 100 percent means that the infestationis exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults obtained can be seen from the following Table 7:

TABLE 7 Podosphaera Test (Protective) Infection as a percentage of theinfection of the untreated control with a concentration of active com-Podosphaera test (systemic) Solvent: 4.7 parts by weight acetoneDispersing agent: 0.3 parts by weight alkylaryl polyglycol ether Water:parts by weight The amount of active compound required for the desiredconcentration of the active compound in the liquid to be used forwatering is mixed with the stated amount of solvent, and the concentrateis diluted with the stated amount of water which contains the statedadditions.

Apple seedlings grown in standard soil are, in the 3 4 leaf stage,watered in one week with 20cc of the liquid to be used for watering, inthe stated concentration of active compound, with reference to 10000 ofsoil. The plants so treated are, after the treatment, inoculated withconidia of Podosphaera leucotricha Salm and placed in a greenhouse at atemperature of 21 23 C and at a relative atmospheric humidity of about70 percent. 10 days after the inoculation, the infection of theseedlings is determined as a percentage of the untreated but alsoinoculated control plants.

0 percent means no infection; percent means that the infection isexactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and theresults obtained can be seen from the following Table 8:

with a concentration of active compound 0f120p.p.m.

Active compound (known) TAB LE 8 Continued Podosphaera Test (systemic)Infection as a percentage of the infection of the untreated control Witha concentration of active com- Active compound pound 01'120 p.p.n1.

EXAMPLE 9 Fusicladium test (apple scab) [Curative] Solvent: 4.7 parts byweight acetone Emulsifier: 0.3 parts by weight alkylaryl polyglycolether Water: 95 parts by weight The amount of active compound requiredfor the desired concentration of the active compound in the spray liquidis mixed with the stated amount of solvent, and the concentrate isdiluted with the stated amount of water which contains the statedadditions.

Young apple seedlings in the 4 6 leaf stage are inoculated with anaqueous conidium suspension of the apple scab causative organismFusicladium dendriticum el and incubated for 18 hours in a humiditychamber at 18 20 C and at an atmospheric humidity of 100 percent. Theplants are then placed in a greenhouse where they dry.

After standing for a suitable period of time, the plants are sprayeddripping wet with the spray liquid prepared in the manner describedabove. The plants are subsequently placed in a greenhouse.

15 days after inoculation, the infestation of the apple seedlings isdetermined as a percentage of the untreated but also inoculated controlplants.

percent means no infestation; 100 percent means that the infestation isexactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds, theperiod of time between inoculation and spraying and the results obtainedcan be seen from the following Table 9:

TABLE 9 Fusicladium Test (Curativc) The following Example illustrates,without limitation, the process for producing the particular newcompounds of the present invention.

EXAMPLE 10 NH--%NH-COOC2H5 NH-C H To 20.2 g (0.1 mole) of2-furoylaminoaniline in cc of dry chloroform are added dropwise, withstirring, 13.1 g (0.1 mole) ethoxycarbonylisothiocyanate, thetemperature being kept to 30 C by cooling with ice. After furtherstirring for one hour, suction filtration is effected. Yield: 20 g (60percent of the theory) N-(2-furoylaminophenyl)-N'-ethoxycarbonylthiourea which can be purified byrecrystallization from acetonitrile. The compound has a melting point ofl56 C.

In analogous manner, the following compounds may be prepared:

N-[2-(thiophen(2)-carbonamido)-phenyl]-N'- methoxycarbonylthiourea,N-[2-(pyridine(3)-carbonamido)-phenyl]-N'-ethoxycarbonylthiourea,N-[2-(pyridine(4)-carbonamido)-phenyl]-N-ethoxycarbonylthiourea andN-[2-(thiazol(4)-carbonamido)-phenyl]-N'-methoxycarbonyl-thiourea. itwill be realized by the artisan that all of the foregoing compoundscontemplated by the present invention possess the desired strongfungicidal properties, with regard to a broad spectrum of activity, aswell as a comparatively low toxicity toward warm-blooded creatures and aconcomitantly low phytotoxicity, enabling such compounds to be used withcorrespondingly favorable Infection as a percentage of the infection ofthe untreated control with 11 concentration of active l 16 changes maybe made without departing from the spirit a o and scope of the presentinvention.

What is claimed is: l. Amidophenylthioureas of the formula:

5 \NHC-H H S H 0 -NH- -NHCOOR O X 4. Compound according to claim 1wherein such N--CR" compound is N-[2-(pyridine(3)-carbonamido)-phenyl]-N'-ethoxycarbonyl-thiourea of the formula s 0 m wh'ch NHii-NH- i-o 01H,-

each X independently stands for a halogen atom,

alkyl with one to four carbon atoms or alkoxy with one to four carbonatoms, 1% I I n stands for 0, l or 2,

R stands for alkyl with one to 12 carbon atoms, N

R stands for a hydrogen atom or alkyl with one to 5. Comp nd ccor ing tclaim 1 wherein such four carbon atoms, and compound isN-[2-(pyridine(4)-carbonamido)-phen- R" stands for furyl or pyridyl.yl]-N '-ethoxycarbonyl-thiourea of the formula 2. Thioureas according toclaim 1 in which X stands for chlorine, bromine, fluorine, methyl,ethyl, i H isopropyl, n-butyl, methoxy, ethoxy or isopropoxy; n NH C NHC 0CH stands for 0 or 1; R stands for methyl, ethyl or isopropyl; Rstands for hydrogen, methyl or ethyl; and R" stands forZ-furyl,2-pyridyl,3-pyridyl, or 4-pyridyl. E m

3. Compound according to claim 1 wherein such compound isN-(2-furoylaminophenyl)-N'-ethoxycar- N bonylthiourea of the formula

1. Amidophenylthioureas of the formula: in which each X independentlystands for a halogen atom, alkyl with one to four carbon atoms or alkoxywith one to four carbon atoms, n stands for 0, 1 or 2, R stands foralkyl with one to 12 carbon atoms, R'' stands for a hydrogen atom oralkyl with one to four carbon atoms, and R'''' stands for furyl orpyridyl.
 2. Thioureas according to claim 1 in which X stands forchlorine, bromine, fluorine, methyl, ethyl, isopropyl, n-butyl, methoxy,ethoxy or isopropoxy; n stands for 0 or 1; R stands for methyl, ethyl orisopropyl; R'' stands for hydrogen, methyl or ethyl; and R'''' standsfor 2-furyl, 2-pyridyl, 3-pyridyl, or 4-pyridyl.
 3. Compound accordingto claim 1 wherein such compound isN-(2-furoylaminophenyl)-N''-ethoxycarbonylthiourea of the formula 4.Compound according to claim 1 wherein such compound isN-(2-(pyridine(3)-carbonamido)-phenyl)-N''-ethoxycarbonyl-thiourea ofthe formula